Instituto Universitario de Tecnología Química CSIC-UPV and Departamento de Química, Universidad Politécnica de Valencia, Av., De los Naranjos s/n, 46022, Valencia, Spain.
Dalton Trans. 2011 Oct 28;40(40):10719-24. doi: 10.1039/c1dt10826c. Epub 2011 Aug 30.
Three MIL-100 (Fe) samples differing in average crystal size (from 60-70 to >400 nm) have been synthesized by microwave heating using three HF/Fe(3+) ratios. Oxidation of diphenylmethane with tert-butylhydroperoxide (TBHP) and thiophenol with oxygen are catalyzed by three MIL-100 (Fe) samples with similar reaction rates regardless of its average particle size. In contrast, the activity of the three MIL-100 (Fe) samples for the oxidation of bulky triphenylmethane by TBHP largely depends on the average crystal size of the sample: the smaller the average particle size, the larger the initial reaction rate of triphenylmethane oxidation. These results show that diffusion limitation takes place on MOF catalysis depending on the substrate size and provides indirect evidence that these reactions take place inside the intracrystalline space of the porous catalysts.
三种平均晶粒尺寸不同的 MIL-100（Fe）样品（从 60-70nm 到>400nm）通过微波加热使用三种 HF/Fe（3+）比合成。二苯甲烷与叔丁基过氧化氢（TBHP）的氧化和硫酚与氧气的氧化由三种平均粒径相似的 MIL-100（Fe）样品催化，反应速率相同。相比之下，三种 MIL-100（Fe）样品对 TBHP 氧化大体积三苯甲烷的活性在很大程度上取决于样品的平均晶粒尺寸：平均粒径越小，三苯甲烷氧化的初始反应速率越大。这些结果表明，扩散限制取决于基质尺寸在 MOF 催化中起作用，并提供了这些反应在多孔催化剂的晶内空间内发生的间接证据。
